KR100446655B1 - Hydrogenation reaction catalyst for preparing gamma-butyrolactone and method for preparing thereof, and method for preparing gamma-butyrolactone using the same - Google Patents

Abstract

The present invention relates to a hydrogenation catalyst for producing gamma butyrolactone, a method for preparing the same, and a method for producing gamma butyrolactone using the same, and particularly, in a hydrogenation catalyst for producing gamma butyrolactone, a silica-titania support including titania The present invention relates to a hydrogenation catalyst for producing gamma butyrolactone on which palladium and nickel are supported, a method for producing the same, and a method for producing gamma butyrolactone using the same.

The hydrogenation catalyst according to the present invention has a higher reaction rate and yield in hydrogenation of maleic anhydride (MAN) under the same conditions than the conventional single-component support using a titania-added support, and shortens the hydrogenation reaction time and uses the catalyst. It is possible to reduce the yield of gamma butyrolactone in economically high yield.

Description

HYDROGENATION REACTION CATALYST FOR PREPARING GAMMA-BUTYROLACTONE AND METHOD FOR PREPARING THEREOF, AND METHOD FOR PREPARING GAMMA-BUTYROLACTONE USING THE SAME}

The present invention relates to a hydrogenation catalyst for producing gamma butyrolactone, a method for producing the same, and a method for producing gamma butyrolactone using the same. More specifically, the active ingredient includes palladium and nickel as a main component, Gamma suitable for application to commercial processes because of the liquid phase reduction of gamma butyrolactone (hereinafter referred to as GBL) from maleic anhydride (hereinafter referred to as MAN) under a catalyst obtained by using the composite compound as a support. It relates to a hydrogenation reaction catalyst for producing butyrolactone, a method for producing the same, and a method for producing gamma butyrolactone using the same.

GBL is used as a starting material in various synthetic methods. In fact, it plays an important role in the production of butyric acid and derivatives, and the production of substances such as tetrahydrofuran and N-methylpyrrolidone. GBL itself is also known as an important solvent in the production of acrylates, polymers and synthetic resins.

At present, the method of preparing GBL mainly converts primary hydrogenated amber anhydrous acid (hereinafter, SAN) from MAN to GBL in the presence of a catalyst through a secondary hydrogenation method.

In the structure of MAN, two unsaturated C═O and one C═C bond are present and the unsaturated bond is saturated with a single bond during hydrogenation. Hydrogenation to SAN is the process of converting unsaturated C═C double bonds to C—C single bonds. This process is exothermic, resulting in about 32 kcal / mol of heat dissipating and no water is produced during the reaction. In general, it is reported that the reaction is completed even in the non-catalyst state, and when the catalyst is used, the reaction conditions are relaxed, and the reaction proceeds at about 110 to 140 ° C. The side reactions obtained by the hydrogenation reaction include butanol, propanol, acetone, and the like, and the degree of side reactions is reported to be intensified when the reaction conditions are high in the presence of a catalyst.

The hydrogenation of two C═O double bonds in the compound, which is the secondary hydrogenation method, is very slow in the reaction rate compared to the primary hydrogenation, and the reaction of tetrahydrofuran and 1,4 butanediol by many side reactions and perhydrogenation depending on the reaction conditions. Many researchers are working to alleviate these reaction conditions and improve the selectivity to GBL because they cause production. The secondary hydrogenation generates heat of reaction of 26 kcal / mol, and unlike primary hydrogenation, water is generated through hydrogenation of oxygen atoms. The production of water leads to the inevitable production of succinic acid (hereinafter, SA), which has a negative effect on yield and process efficiency.

The liquid phase hydrogenation reaction is carried out at a temperature of about 700 to 1500 psig, 180 to 250 ℃. The route of the side reactants is sensitive to the reaction conditions, in particular the reaction temperature. When the reaction temperature is 180 ° C. or lower, the reaction rate is remarkably lowered, and the effects of condensation and adsorption decrease the catalytic activity. In addition, the rate of SA production by water produced by hydrogenation is significantly increased. This is caused by the difference in reaction rate between SAN, water, and hydrogen, because the SAN in the reactant prefers the reaction with water unless the SAN is rapidly converted to GBL. On the other hand, at a temperature of 250 ° C or higher, the production rate of GBL increases, but the side reaction rate also increases. Based on the research results thus far, it is well known that MAN, SAN and GBL can also undergo decomposition reactions under hydrogenation catalysts and conditions, and in fact, substances containing C ₂ -C ₃ are present in the product. . So-called hydrogenolysis is described as a mechanism that explains the production of these substances. In addition, as a secondary result of the decomposition reaction, condensation and polymerization occur, and this continuous effect produces various high boiling materials.

On the other hand, there are known applications of various catalysts to effectively obtain GBL through hydrogenation from MAN. As an effective catalyst known to date, a multicomponent catalyst composed of noble metals and transition metals based on palladium is known. For example, U.S. Patent No. 5,536,849 proposed a catalyst having chromium and silica as a main component of copper as a main component, and this catalyst improves the problem of unreduction of a large amount of SAN, which has been a problem until now. However, the environmentally fatal disadvantage of chromium has shown problems in the treatment of waste catalysts. Recently, US Pat. No. 6,008,375 introduced a catalyst substituted with aluminum and graphite instead of chromium.

As mentioned in US Pat. No. 5,118,821, as the noble metal hydrogenation catalyst, silica (SiO ₂ ) or activated carbon is mainly used as a support based on the active component of Pd / Ni. Recently, it has been reported that the addition of molybdenum as a third component improves the activity and selectivity (Korean Patent Application No. 2001-95500). However, in the results so far, the reaction time from MAN to GBL takes more than 3 hours, and the amount of catalyst to the reactants occupies 10 to 15% by weight, thus limiting the applicability of the practical method and after preparing gamma butyrolactone. It was cumbersome and complicated in the process to separate the THF used as solvent.

In view of the above problems in the prior art, the present invention provides a silica support having a surface property modified by the addition of titania in a method for producing gamma butyrolactone (GBL) by liquid-hydrogenating maleic anhydride (MAN). It is an object of the present invention to provide a hydrogenation catalyst for producing gamma butyrolactone having improved activity and selectivity under harsh conditions and a method of preparing the same.

Another object of the present invention is to provide a method for economically producing gamma butyrolactone by minimizing the amount of reaction and reaction time of the catalyst for the reactants using the hydrogenation reaction catalyst.

The present invention, in order to achieve the above object, in the hydrogenation catalyst for producing gamma butyrolactone,

Provided is a hydrogenation catalyst for preparing gamma butyrolactone on which a palladium and nickel are supported on a silica-titania support including titania.

In addition, the present invention comprises the steps of a) dissolving an alcohol precursor comprising titania in a non-aqueous solvent, supported on mesoporous silica and calcined to prepare a silica-titania support; And

b) adding the silica-titania support of a) to an aqueous solution in which the precursors of palladium and nickel are dissolved, stirring, removing the solvent, drying and calcining

It provides a method for producing a hydrogenation catalyst for producing gamma butyrolactone comprising a.

In addition, the present invention provides a method for producing gamma butyrolactone comprising the step of hydrogenating maleic anhydride in a liquid phase,

The hydrogenation reaction provides a method for preparing gamma butyrolactone, which is carried out under a hydrogenation reaction catalyst and a gamma butyrolactone solvent in which palladium and nickel are supported on a silica-titania support including titania.

Hereinafter, the present invention will be described in detail.

The present invention relates to a hydrogenation catalyst for producing gamma butyrolactone prepared using a support added with titania, and a method for preparing the same, and a method for producing gammabutyrolactone from maleic anhydride (MAN) using the same.

The method for producing a hydrogenation catalyst of the present invention consists of a process of supporting palladium and nickel using a silica support modified by titania. The hydrogenation catalyst used in the present invention is characterized by showing a higher reaction rate and yield in hydrogenation of maleic anhydride (MAN) under the same conditions than a conventional single-component support using a titania-added support.

The silica-titania support of the present invention dissolves an alcoholic precursor containing titania in a non-aqueous solvent such as toluene and attaches to silica having mesopores to form a composite of titania and silica on all surfaces including the pore surface. It is then produced by firing.

Then, the silica-titania support prepared above is supported by an aqueous solution of precursors such as nitrate and hydrochloride of palladium and nickel to prepare a hydrogenation catalyst. In the method of supporting palladium and nickel, an aqueous solution containing palladium and nickel is prepared at a temperature of 50 to 80 ° C., and then added to and mixed with a silica-titania support, and water, which is a solvent, is removed under vacuum. The solid obtained above is dried and then calcined at a temperature of 400 to 500 ° C. The catalyst obtained by such a process is preferably used after reduction in the presence of hydrogen and 350 to 600 ℃ temperature before the hydrogenation reaction.

Titania used in the support of the present invention is used in 1 to 50 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of silica. If the amount of titania is less than 1 part by weight, the degree of dispersion becomes large, but there is a problem in that the benefits of titania do not appear. If the amount of titania exceeds 50 parts by weight, there is a problem in that titania crystals are formed.

In addition, the silica used as the support in the present invention is preferably used mesoporous silica having a surface area of 200 to 1500 m 2 and pore conditions of 2 to 50 nm.

In addition, palladium used as an active ingredient in the catalyst of the present invention is used in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the total catalyst weight of the support and the catalyst component. If the amount of the palladium is less than 0.1% by weight, there is a problem in that the activity is poor due to the insignificant hydrogenation ability, and when the amount of the palladium is used in excess of 5% by weight, there is a problem in that the catalyst production ratio due to the use of precious metals is increased while there is almost no increase in activity.

The nickel content is used in an amount of 5 to 30% by weight, preferably 15 to 25% by weight, based on the total catalyst weight of the support and the catalyst component. If the amount of the nickel is less than 5% by weight, there is a problem in that the activity is poor because the hydrogenation capacity is insignificant.

On the other hand, the present invention can produce gamma butyrolactone (GBL) through the hydrogenation reaction using the hydrogenation reaction catalyst obtained above.

Conventionally, the method is complicated by re-separating and recovering a solvent such as THF after preparing gamma-butyrolactone, but the present invention does not require a solvent separation method by using gamma-butyrolactone, which is a product of gamma-butyrolactone, as a solvent. It is economical. In addition, the present invention can shorten the reaction time by increasing the activity per g catalyst during the hydrogenation reaction. Therefore, the present invention not only obtains excellent results in the reaction results but also has a great advantage in the application part of the actual reaction process by shortening the reaction time compared to the conventional methods.

Hydrogenation of maleic anhydride (MAN) to obtain GBL in the present invention is preferably carried out under the conditions of temperature of 180 to 250 ℃, pressure of 700 to 1500 psig, and reaction time of 1 to 2 hours.

In particular, the amount of the hydrogenation reaction catalyst of the present invention is preferably used in an amount of 3 to 10 parts by weight based on 100 parts by weight of maleic anhydride as a reactant, and more preferably 3 to 5 parts by weight due to the high activity of the catalyst. If the amount of the catalyst is less than 3 parts by weight, there is a problem of increasing the polymer due to the increase of the reaction time, and if it exceeds 10 parts by weight, there is a problem that the total carbon content is sharply reduced.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, an Example is for illustrating this invention and is not limited only to these.

Example 1

Titania isopropyl oxide containing 10% by weight of titania was quantified, dissolved in a solvent of toluene, supported on 20 g of mesoporous silica and calcined at 450 ° C.

The calcined titania-added silica support was placed in an aqueous solution in which 1.26 g of palladium nitrate and 14.23 g of nickel nitrate were dissolved, followed by stirring. Then, the solvent was removed. Then, after drying at a temperature of 110 ℃ calcined at 450 ℃ and the catalyst was reduced by using hydrogen at the same temperature. The final compositions of palladium and nickel on the catalyst are 2.0% and 16.3% by weight, respectively.

Into a 300 ml high-pressure reactor, 80 g of maleic anhydride (MAN), 120 g of GBL, and 4 g of the catalyst were added, followed by raising the temperature to 230 ° C. at a temperature rising rate of 20 ° C./min at a pressure of 1300 psig. The reaction proceeded. The reactants were analyzed by gas chromatography with a flame ionization detector. After 2 hours, the conversion of maleic anhydride (MAN) was 100% and the yield of gamma butyrolactone (GBL) was 74%. .

Example 2

It carried out in the same manner as in Example 1, but carried out a hydrogenation reaction at a temperature of 200 ℃. After 2 hours, the maleic anhydride (MAN) conversion was 100% and the yield of GBL was 14%.

Comparative Example 1

This comparative example was made to show the effect of titania added to the support. A catalyst was prepared by supporting palladium and nickel as in the method described in Example 1, using a titania-free mesoporous silica support. The compositions of palladium and nickel on the catalyst are 2.0% and 16.3% by weight, respectively.

After 2 hours of reaction under the same conditions as in Example 1, the conversion of MAN was 100% and the yield of GBL was 7%.

Comparative Example 2

In this comparative example, it was made to show the effect of the silica support used in the support. Using a commercial silica support (Junsei Co.) excluding titania, a catalyst was prepared by supporting palladium and nickel as in the method described in Example 1. The compositions of palladium and nickel on the catalyst are 2.0% and 16.3% by weight, respectively.

After 2 hours of reaction under the same conditions as in Example 1, the conversion of MAN was 100% and the yield of GBL was 4%.

As described above, the hydrogenation catalyst according to the present invention shows a higher reaction rate and yield in hydrogenation of maleic anhydride (MAN) under the same conditions than the conventional single-component support using a titania-added support. It is possible to shorten the amount of the catalyst used and to obtain economically high yield of gamma butyrolactone. In addition, when the gamma butyrolactone is prepared using the hydrogenation reaction catalyst and using the same gamma butyrolactone as a solvent, there is no hassle of solvent separation, and in particular, the reaction time can be shortened by increasing the activity per g of catalyst.

Claims (7)

In the hydrogenation catalyst for producing gamma butyrolactone, A hydrogenation catalyst for preparing gamma butyrolactone, in which palladium and nickel are supported on a silica-titania support including titania. The hydrogenation catalyst for producing gamma butyrolactone according to claim 1, wherein the titania content of the silica-titania support is 1 to 50 parts by weight based on 100 parts by weight of silica. The method of claim 1, wherein the silica-titania support is prepared by supporting and firing an alcohol precursor including titania dissolved in a non-aqueous solvent in mesoporous silica having a surface area of 200 to 1500 m 2 and pores of 2 to 50 nm. A hydrogenation catalyst for producing gamma butyrolactone. According to claim 1, wherein the content of the palladium is 0.1 to 5% by weight based on the total catalyst weight of the support and the catalyst component, the nickel content is 5 to 30% by weight relative to the total catalyst weight of the support and the catalyst component Hydrogenation catalyst for producing gamma butyrolactone. a) preparing a silica-titania support by dissolving an alcohol precursor comprising titania in a non-aqueous solvent, immersing in mesoporous silica, and calcining; And b) adding the silica-titania support of a) to an aqueous solution in which the precursors of palladium and nickel are dissolved, stirring, removing the solvent, drying and calcining Method for producing a hydrogenation catalyst for producing gamma butyrolactone comprising a. In the manufacturing method of gamma butyrolactone comprising the step of hydrogenating maleic anhydride in a liquid phase, The hydrogenation reaction is a method for producing gamma butyrolactone, which is carried out under a hydrogenation catalyst and a gamma butyrolactone solvent in which palladium and nickel are supported on a silica-titania support including titania. The method of claim 6, wherein the hydrogenation reaction catalyst is used in an amount of 3 to 10 parts by weight based on 100 parts by weight of maleic anhydride (MAN).